CN102660019B - High temperature-resistant nylon/ polybutylece terephthalate (PBT)/polyethylene terephthalate (PET) copolymer, and preparation method and application thereof - Google Patents
High temperature-resistant nylon/ polybutylece terephthalate (PBT)/polyethylene terephthalate (PET) copolymer, and preparation method and application thereof Download PDFInfo
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- CN102660019B CN102660019B CN 201210143112 CN201210143112A CN102660019B CN 102660019 B CN102660019 B CN 102660019B CN 201210143112 CN201210143112 CN 201210143112 CN 201210143112 A CN201210143112 A CN 201210143112A CN 102660019 B CN102660019 B CN 102660019B
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Abstract
The invention discloses a high temperature-resistant nylon/ polybutylece terephthalate (PBT)/polyethylene terephthalate (PET) copolymer, and a preparation method and application thereof. The copolymer consists of 75 to 99 percent of high-temperature nylon, 0.85 to 23.75 percent of PBT, and 0.05 to 3.75 percent of PET; the high-temperature nylon is a high-temperature nylon unit which is formed by reacting PBT, PET and diamine; and the diamine is linear chain aliphatic diamine, branched chain aliphatic diamine or alicyclic diamine. Compared with the corresponding benzene ring homopolymer, the copolymer has the advantages that the copolymer is high in impact resistance and flowing performance, and the electrical property is greatly improved.
Description
Technical field
The invention belongs to the modified plastics field, be specifically related to a kind of high temperature resistant nylon/polybutylene terephthalate (PBT)/polyethylene terephthalate (PET) multipolymer and preparation method thereof and application.
Background technology
Fatty polyamide, such as PA6, PA66, have excellent physical strength, thermotolerance, chemical proofing, wearability and self lubricity, and frictional coefficient is low, its Application Areas comprises electronic apparatus, trolley part, furniture, building materials and fiber, has become one of most important engineering plastics.
In the last few years, along with the development of situation, required electronics, electrical equipment, associating information device miniaturization, high performance, the requirement of material was further strengthened.Particularly along with surface mounting technique (Surface Mount Technology, abbreviation SMT) development, the various electric elements such as junctor, switch, rly., electrical condenser are installed simultaneously, are connected in the circuit board, promoted electronic component miniaturization, densification, construction costs reduced by 20～30% than former product.But, adopting the SMT technology, each electric elements and circuit base plate are wanted heat in infrared heating device simultaneously, and soldering resistance and the dimensional stability of the material of making each element and wiring board are had higher requirement.Be environmental contamination reduction, existing advocating energetically used lead-free scolding tin.The fusing point of lead in the past-soldering tin is at 183 ℃, and novel scolding tin is tin-copper-silver soldering tin, and fusing point is 215 ℃, and fusing point material has than before improved 30 ℃, and at this moment the thermotolerance of PA6, PA66 just can not meet the demands.Therefore developing the higher material of thermotolerance just becomes inevitable.
Semiaromatic polyamide composition is with the diamines of aromatic nucleus or dicarboxylic acid and aliphatic dicarboxylic acid or diamines, through the prepared polyamide resin of polycondensation, is a kind of in the aromatic polyamide.Owing in the polymeric amide molecular backbone chain, imported aromatic nucleus, thereby thermotolerance and mechanical property have been improved, reduced water-intake rate, and more suitable P/C ratio is arranged, be the high resin of thermotolerance between general engineering plastic high temperature resistant nylon and thermostability engineering plastic PEEK, be mainly used in automobile and electric and electronic industry.Develop rapidly along with high-tech, its application has new breakthrough and progress, and the market requirement is in rising trend.But the shock strength of semiaromatic polyamide composition and mobile relatively poor is difficult for during injection moulding filling with.
Patent JP57200420, JP58111829, EP1074585A1, CN1624021A disclose the preparation method of polymeric amide MXD6.In the method that proposes, in batch reactor aromatic diamine is added drop-wise in the aliphatic dicarboxylic acid of melting, the water that the system temperature that raises is simultaneously removed the condensation generation carries out polyreaction.CN1451677A has described the solid-phase tack producing method of a kind of polymeric amide MXD6, preserves under given conditions polymeric amide, even initial polymeric amide is rear to spending 20 days solid-phase tack producing or the longer time from preparing, the polymeric amide MXD6 Huang degree that makes is very low.
Because the fusing point of polyamide 6 T has exceeded its decomposition temperature, must add the 3rd monomer to reduce fusing point.Polyamide 6 T multipolymer is by the dicarboxylic acid component who mainly is comprised of terephthalic acid and m-phthalic acid or hexanodioic acid and is mainly obtained by the diamine components polycondensation of 1,6-hexanediamine composition.The amide group concentration of polyamide 6 T multipolymer is higher, can cause chemical proofing, water absorption resistance, the melt-processed less stable of polymkeric substance.Add the 3rd a large amount of monomers and reduced the degree of crystallinity of polymkeric substance, also can cause thermotolerance, chemical proofing, water absorption resistance and the dimensional stability of polymkeric substance to descend.
Patent US5516882, US5981692 and US962628 have described with terephthalic acid, m-phthalic acid, 1,6-hexanodioic acid, 1,6-hexanediamine and 2-methyl isophthalic acid, 5-pentamethylene diamine are main raw material, come the method for synthesizing polyamides 6T multipolymer by the high-temperature fusion polymerization more than 300 ℃.Patent US6140459 has described with terephthalic acid, 1, and 6-hexanediamine and another kind of aliphatic long-chain di-carboxylic acid are raw material, come synthesizing polyamides 6T multipolymer by melt polymerization.Yet when adopting melt polymerization to prepare semiaromatic polyamide composition, the secondary polymerization reaction temperature can surpass the fusing point of polymkeric substance, and overstand at high temperature, the DeR of various side reactions and polymkeric substance is violent, the phenomenon that causes easily polymkeric substance tone variation, physical strength reduction and formability to degenerate.
Patent US5663284 discloses a kind of method for preparing polyamide 6 T/66 polymkeric substance, first carry out first-stage polymerization having under the condition that water exists, temperature of reaction is lower than melting point polymer, keep pressure by make up water in autoclave when discharging, prepolymer obtains high viscosity polymer by vented twin-screw extruder melting tackify.But in order to obtain satisfying the prepolymer of melting tackify requirement, the prepolymerization temperature has approached the fusing point of polymkeric substance, to improve the limiting viscosity of prepolymer.
In the prior art, patent US6133406 has proposed a kind of polymerization technique of semiaromatic polyamide composition: first under the condition that has water to exist, prepolymer at the synthetic low limiting viscosity of lower temperature, then through the prepolymer of the higher limiting viscosity of solid-phase tack producing reaction preparation, melt extrude the polymkeric substance that tackify obtains high limiting viscosity through twin screw again.This route relates to prepolymerization, solid-phase tack producing, melting tackify polystep reaction, requires complicated production stage and equipment.
Among the patent US6156869, after obtaining prepolymer, can obtain the polyamide 9T resin by long solid-phase tack producing, this technical requirements prepolymer has higher limiting viscosity.Polyamide 9T has higher degree of crystallinity, dimensional stability and lower water-intake rate.
In the prior art, obtain the semiaromatic polyamide composition prepolymer of higher limiting viscosity, can realize by the water that improves the prepolymerization temperature or discharge in the prepolymerization system.Raising prepolymerization temperature can cause the generation of side reaction, also can improve reaction pressure, to the also corresponding raising of requirement of equipment.The water of discharging in the reaction can vapor away unreacted diamine, and the result causes the monomeric unit ratio of prepolymer greatly different with the initial monomers ratio that joins reactor, can not guarantee the molar ratio balance of monomer di-carboxylic acid and diamine.
First monomer is made salt, be synthesized by polycondensation the loss that semiaromatic polyamide composition just can be avoided diamine by salt again.Patent US5663284 judges the terminal point of salt-forming reaction by measuring the pH value, prepare semiaromatic polyamide composition with salt.
When the synthetic fat polyamide, for the ease of the molar ratio of control di-carboxylic acid, diamine, and remove impurity in the monomer, the method that salt carries out polycondensation is again made first in employing usually.During preparation fatty polyamide salt, usually first in aqueous solvent or alcohol, carry out neutralization reaction, then separate, purify, drying and obtaining.
The report that improves shock resistance, streamer performance and the electrical property of material by preparation high temperature resistant nylon/PBT/PET multipolymer is not arranged at present, add the cost that PET can reduce multipolymer, material shock resistance, streamer performance and electrical property are kept simultaneously.
Summary of the invention
For the shortcoming and deficiency that overcome prior art, primary and foremost purpose of the present invention is to provide a kind of high temperature resistant nylon/PBT/PET multipolymer, and this multipolymer has preferably shock resistance and streamer, and electrical property also is improved.
Another object of the present invention is to provide the preparation method of above-mentioned high temperature resistant nylon/PBT/PET multipolymer.
A further object of the present invention is to provide the purposes of above-mentioned high temperature resistant nylon/PBT/PET multipolymer.
Purpose of the present invention is achieved through the following technical solutions:
A kind of high temperature resistant nylon/PBT/PET multipolymer is grouped into by the one-tenth of following molar percentage:
High-temperature nylon: 75-99%
PBT：0.85-23.75%
PET：0.05-3.75%；
Described high-temperature nylon is the high-temperature nylon unit that PBT, PET and diamine reactant generate;
Described diamines is straight chain aliphatic diamine, side chain aliphatic diamine or cycloalphatic diamine;
Described straight chain aliphatic diamine is Putriscine, 1,6-hexanediamine, 1,8-octamethylenediamine, 1,9-nonamethylene diamine, 1，10-diaminodecane, 1,11-11 carbon diamines or 1,12-, 12 carbon diamines;
Described side chain aliphatic diamine is the 2-methyl isophthalic acid, 5-pentamethylene diamine, 3-methyl isophthalic acid, 5-pentamethylene diamine, 2,4-dimethyl-1,6-hexanediamine, 2,2,4-trimethylammonium-1,6-hexanediamine, 2,4,4-trimethylammonium-1,6-hexanediamine, 2-methyl isophthalic acid, 8-octamethylenediamine or 5-methyl isophthalic acid, 9-nonamethylene diamine;
Described cycloalphatic diamine is cyclohexane diamine, methylcyclohexane diamines or 4,4 '-diamino-dicyclohexyl methane.
Described high temperature resistant nylon/PBT/PET multipolymer can also comprise oxidation inhibitor, lubricant, nucleator, fire retardant, tinting material, softening agent, static inhibitor; Also can strengthen Properties of the copolymers by adding glass fibre, carbon fiber, mineral filler.
The fusing point of described high temperature resistant nylon/PBT/PET multipolymer is 270-330 ℃, and solution solvent viscosity ratio η is 1.5-2.5, and content of carboxyl end group is 15-100mol/t, and terminal amino group content is 15-100mol/t.
The preparation method of above-mentioned high temperature resistant nylon/PBT multipolymer may further comprise the steps:
Get polybutylene terephthalate (PBT), polyethylene terephthalate (PET) and diamines and be dissolved in the solvent, 180 ~ 280 ℃ of lower polyreaction 6-18h obtain high temperature resistant nylon/PBT/PET multipolymer; The mol ratio of described PBT, PET and diamines is (85-95): (5-15) (75-99);
Described solvent is alcoholic solution, N-Methyl pyrrolidone, dimethyl formamide, dimethyl sulfoxide (DMSO), dimethyl sulfone, diethyl sulfone, diethyl sulfoxide, di-isopropyl sulfone, sulfobenzide, tetramethylene sulfone or tetramethyl-sulfone.
Above-mentioned high temperature resistant nylon/PBT/PET multipolymer can replace the bearing of steel, and can be applicable in mower, the cutting machine.
High temperature resistant nylon of the present invention/PBT/PET multipolymer has preferably, and shock resistance, streamer and electrical property are because introduced PBT in structure.Its reaction principle is as follows:
The present invention has following advantage and effect with respect to prior art:
Its corresponding phenyl ring homopolymer of multipolymer of the present invention is compared, and has preferably shock resistance and streamer, and electrical property also is improved.
Embodiment
The present invention is described in further detail below in conjunction with embodiment, but embodiments of the present invention are not limited to this.
The relevant performance perameter of product is measured by the following method in the embodiment of the invention:
Shock strength is pressed DIN EN ISO 8256-2005 and is measured.
Volume specific resistance is pressed GBT 1410-2006 and is measured.
Dielectric properties are pressed DIN 53483-1-1969 and are measured.
Helical is long: adopt sea day HT-86 type injection moulding machine, and injection pressure 50MPa, speed 50% is injected 50 moulds continuously, and it is long to survey helical.
Fusing point Tm is by Perkin Elmer DSC-6 analysis-e/or determining.
The component of product is by infrared measurement.
Embodiment 1-4
The preparation method of a kind of high temperature resistant nylon/PBT/PET multipolymer may further comprise the steps
Add PBT, PET, 1 in being furnished with the 20L autoclave pressure of magnetic coupling stirring, prolong, gas phase mouth, charging opening, 6-hexanediamine, tetramethylene sulfone heat up behind the nitrogen purging.Under agitation be warmed up to 230 ℃, reacted 12 hours, cooling discharge obtains high temperature resistant nylon/PBT/PET multipolymer.Performance is shown in Table 1 as a result.
Table 1
As seen from Table 1, multipolymer of the present invention is compared with corresponding homopolymer has preferably shock resistance and streamer, and electrical property also is improved.
Above-described embodiment is the better embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (4)
1. the preparation method of high temperature resistant nylon/PBT/PET multipolymer is characterized in that may further comprise the steps:
Get PBT, PET and diamines and be dissolved in the solvent, 180 ~ 280 ℃ of lower polyreaction 6-18h obtain high temperature resistant nylon/PBT/PET multipolymer; The mol ratio of described PBT, PET and diamines is (85-95): (5-15): (75-99);
Prepared high temperature resistant nylon/PBT/PET multipolymer is that the one-tenth by following molar percentage is grouped into:
High-temperature nylon: 75-99%
PBT： 0.85-23.75%
PET： 0.05-3.75%；
Described high-temperature nylon is the high-temperature nylon unit that PBT, PET and diamine reactant generate.
2. the preparation method of high temperature resistant nylon according to claim 1/PBT/PET multipolymer, it is characterized in that: described diamines is straight chain aliphatic diamine, side chain aliphatic diamine or cycloalphatic diamine.
3. the preparation method of high temperature resistant nylon according to claim 2/PBT/PET multipolymer is characterized in that:
Described straight chain aliphatic diamine is Putriscine, 1,6-hexanediamine, 1,8-octamethylenediamine, 1,9-nonamethylene diamine, 1，10-diaminodecane, 1,11-11 carbon diamines or 1,12-, 12 carbon diamines;
Described side chain aliphatic diamine is the 2-methyl isophthalic acid, 5-pentamethylene diamine, 3-methyl isophthalic acid, 5-pentamethylene diamine, 2,4-dimethyl-1,6-hexanediamine, 2,2,4-trimethylammonium-1,6-hexanediamine, 2,4,4-trimethylammonium-1,6-hexanediamine, 2-methyl isophthalic acid, 8-octamethylenediamine or 5-methyl isophthalic acid, 9-nonamethylene diamine;
Described cycloalphatic diamine is cyclohexane diamine, methylcyclohexane diamines or 4,4 '-diamino-dicyclohexyl methane.
4. the preparation method of high temperature resistant nylon according to claim 1/PBT/PET multipolymer, it is characterized in that: described solvent is alcoholic solution, N-Methyl pyrrolidone, dimethyl formamide, dimethyl sulfoxide (DMSO), dimethyl sulfone, diethyl sulfone, diethyl sulfoxide, di-isopropyl sulfone, sulfobenzide, tetramethylene sulfone or tetramethyl-sulfone.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 201210143112 CN102660019B (en) | 2012-05-09 | 2012-05-09 | High temperature-resistant nylon/ polybutylece terephthalate (PBT)/polyethylene terephthalate (PET) copolymer, and preparation method and application thereof |
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| CN 201210143112 CN102660019B (en) | 2012-05-09 | 2012-05-09 | High temperature-resistant nylon/ polybutylece terephthalate (PBT)/polyethylene terephthalate (PET) copolymer, and preparation method and application thereof |
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| CN102660019B true CN102660019B (en) | 2013-10-23 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102875802A (en) * | 2012-10-11 | 2013-01-16 | 南昌博生复合材料有限公司 | High-impact and heat-resistant copolymer and preparation method thereof |
| CN103881087B (en) * | 2014-03-21 | 2016-05-25 | 山东广垠新材料有限公司 | High temperature resistant nylon/PTT/PEIP/PBIP copolymer and its preparation method and application |
| CN109825065B (en) * | 2019-01-24 | 2021-06-25 | 绍兴振荣汽车零部件有限公司 | Preparation process of sensor shell |
| CN115197416B (en) * | 2022-08-19 | 2024-03-22 | 鞍山七彩化学股份有限公司 | Continuous solid phase polycondensation method for producing PA46 and PA MXD6 |
| CN116285257B (en) * | 2023-05-18 | 2023-07-18 | 广东永鑫华新型材料有限公司 | Preparation method of high-temperature-resistant super-tough modified PBT-PET composite material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1214712A (en) * | 1996-02-05 | 1999-04-21 | 伊斯曼化学公司 | Polyester/polyesteramide blends |
| EP1359180A2 (en) * | 1999-06-29 | 2003-11-05 | M & S Research and Development Co., Ltd. | Method of producing polyamide resin wherein carboxylic acid-activator and/or inorganic salt is present in reaction system therefor |
| CN1772791A (en) * | 2005-11-04 | 2006-05-17 | 东华大学 | Solid phase polymerization process for preparing ethylene telephthalate and aromatic diamine copolymer |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1214712A (en) * | 1996-02-05 | 1999-04-21 | 伊斯曼化学公司 | Polyester/polyesteramide blends |
| EP1359180A2 (en) * | 1999-06-29 | 2003-11-05 | M & S Research and Development Co., Ltd. | Method of producing polyamide resin wherein carboxylic acid-activator and/or inorganic salt is present in reaction system therefor |
| CN1772791A (en) * | 2005-11-04 | 2006-05-17 | 东华大学 | Solid phase polymerization process for preparing ethylene telephthalate and aromatic diamine copolymer |
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